EP2181074B1 - Neue röntgendichte glasfasern und zahnprothesenelement mit diesen fasern - Google Patents

Neue röntgendichte glasfasern und zahnprothesenelement mit diesen fasern Download PDF

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Publication number
EP2181074B1
EP2181074B1 EP08829145A EP08829145A EP2181074B1 EP 2181074 B1 EP2181074 B1 EP 2181074B1 EP 08829145 A EP08829145 A EP 08829145A EP 08829145 A EP08829145 A EP 08829145A EP 2181074 B1 EP2181074 B1 EP 2181074B1
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European Patent Office
Prior art keywords
glass
content
previous
glass thread
fibers
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EP08829145A
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English (en)
French (fr)
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EP2181074A2 (de
Inventor
Anne Berthereau
Jérôme BLAIZOT
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Recherches Techniques Dentaires - Rtd Ste
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Recherches Techniques Dentaires - Rtd Ste
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C03C13/001—Alkali-resistant fibres
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C03C13/001—Alkali-resistant fibres
    • C03C13/002—Alkali-resistant fibres containing zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
    • C03C4/087—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for X-rays absorbing glass

Definitions

  • the present invention relates to glass threads or fibers, these threads being capable of being produced by a process consisting of mechanically stretching molten glass threads flowing from orifices arranged at the base of a die generally heated by Joule effect. .
  • glass son having ionizing radiation absorption properties, especially X-rays, thanks to their new, particularly advantageous composition.
  • the new glass fibers of the invention find a particularly advantageous application in the dental field, in particular as fibers constituting a prosthetic element.
  • the prosthetic elements within the meaning of the invention cover two types of products. Firstly, products made by machining profiles or rods made of glass fibers embedded in a resin matrix, such as, in particular, dental posts, intradentinal posts, bridges, and preforms. for CAD / CAM. It is then fiberglass woven to form a strip, which is then impregnated with a resin. These strips known in the dental field under the English expression "prepreg” also serve as bridge reinforcement or "splinting". In practice, the polymerization of the resin impregnating the prepregs is carried out by the practitioner or the prosthetist by light-curing.
  • the invention is more particularly described in relation to the dental posts of composite material although, as already said, it can be applied to all the prosthetic elements listed above.
  • the dental posts are used for the reconstruction of depilated teeth.
  • Metal posts are usually made of stainless steel. They have the main disadvantages of being subject to corrosion phenomena. In addition, they have a transverse modulus of elasticity different from that of the dentine to lead, eventually, to a separation of the tenon.
  • EP-A-0 432 001 of the Applicant are in practice made of unidirectional long fibers of glass or carbon embedded in a biocompatible resin matrix. In general, the proportion of long fibers whatever the chosen material, represents 40 to 80% by volume of the tenon, the complement to 100% being occupied by the matrix.
  • the document EP-A-0 895 774 discloses reinforcing elements for dental restoration in which the metal oxides are incorporated directly into the fiberglass.
  • the so-called AR fiber containing, as radiopaque metal oxide, zirconia (ZrO 2 ) at a content of between 1 and 20% by weight is more particularly known.
  • ZrO 2 zirconia
  • the only fiber used in dentistry for its radio opacity properties is its mechanical strength which is lower compared, for example, with that of the fiber E also listed in the aforementioned document. The latter is not radio-opaque and is not used for this property.
  • Another disadvantage of the AR fiber remains its level of radiopacity which is not clinically satisfactory.
  • the tenon can sometimes be confused with the dentin on the radiography, especially when the thickness of the dentinal wall is 2 to 3 mm. The diagnosis becomes difficult when the practitioner reviews his previous intervention.
  • the level of radio opacity is sufficient to identify the accidental ingestion of a tenon.
  • Another disadvantage of the AR fiber lies in its high refractive index, of the order of 1.56. Therefore, to obtain a translucent post, it is necessary, as indicated in the document WO-01/08590 to increase accordingly the index of refraction of the matrix, which necessarily limits the choice of its components.
  • the zirconium oxide is difficult to miscible with the other oxides present in the glass fibers, making delicate fiber drawing operations and more generally the manufacture of these fibers.
  • the problem to be solved by the invention is therefore to develop fibers that are alternatives to the AR fibers as well as their manufacturing process, that is to say a glass composition that can be fiberized with a sufficient forming margin and whose mechanical properties, and radio opacity are together, higher than those of AR fibers.
  • the temperature at which the most refractory crystal appears in a system with thermodynamic equilibrium is called “liquidus temperature”, denoted “ liq ".
  • the liquidus temperature thus gives the lower limit at which it is possible to fiber.
  • the forming margin is defined as the difference between the temperature at which the viscosity of the glass is 1000 Poises (100 Pa), the temperature at which the glass is generally fiberized, and the liquidus temperature.
  • the forming margin is greater than 50 ° C.
  • the document US2007 / 0042172 describes glass compositions for use in batteries.
  • the composition C-5 in particular describes a composition whose sum of Na 2 O + K 2 O + Li 2 O is greater than 12 making it possible to limit the devitrification and to reduce the viscosity of the glass.
  • such a high content of alkaline oxides gives the fiber hydrophilic properties that can cause water infiltration phenomena in the composite.
  • the mere presence of ZrO 2 and ZnO is not sufficient to give the fiber radio opacity properties.
  • the subject of the invention is a glass wire comprising a plurality of filaments, the chemical composition of which comprises the following constituents within the limits defined below, expressed in weight percentages: SiO 2 40 to 60 Al 2 O 3 0 to 5 CaO 1 to 15 MgO 1 to 15 BaO 2 to 15 SrO 12 to 20 ZnO 0.5 to 10 Na 2 O + K 2 O + Li 2 O 0 to 5 TiO 2 3 to 20
  • Silica (SiO 2 ) is a forming oxide of the vitreous network, and plays an essential role for its stability. Within the limits defined above, when the percentage of this constituent is less than 40%, the glass obtained is not sufficiently viscous and devitrifies too easily during fiber drawing. For contents greater than 60%, the glass becomes viscous and more difficult to melt. As a result, the silica content is preferably between 48 and 55%.
  • Alumina (Al 2 O 3 ) is also a formator of the network of glasses according to the invention, but is nevertheless detrimental to the properties of devitrification.
  • the alumina content is preferably between 3 and 4%.
  • Lime (CaO) and magnesia (MgO) make it possible to regulate the viscosity and to control the devitrification of the glasses according to the invention. They have a particularly appreciable melting effect in compositions which are low in alkaline oxides.
  • a CaO content greater than or equal to 15% causes an increase in devitrification rates CaSiO 3 (wollastonite) detrimental to good fiber drawing.
  • the CaO content is preferably between 5 and 6%.
  • the MgO content is preferably between 4 and 7%.
  • the oxides of barium (BaO) and strontium (SrO) are essential because their presence makes it possible to solve the technical problems on which the present invention is based, and furthermore provide several additional advantages. It has indeed been observed that the presence of BaO and SrO makes it possible to confer a strong absorption of ionizing radiation, in particular X-rays. The presence of these two oxides is essential because there is a synergistic effect between them, which allows to obtain higher X-ray absorption when only one of these oxides is used.
  • Barium is an atom which gives an absorption mass coefficient among the highest possible for an energy of 40 keV or 60 keV, while for an energy of 20 keV the strontium absorbs more than the barium and is among the atoms the more absorbent.
  • the simultaneous presence of the two atoms thus makes it possible to obtain a strong absorption over a wide range of energies, in this case the entire X-ray spectrum (from 100 eV to 100 keV).
  • strontium oxide has the advantage of increasing the tenacity and the Young's modulus of the fibers as well as improving the forming margin of the glass, thus facilitating fiber drawing.
  • barium oxide has the disadvantage of increasing the density of the glass.
  • the BaO content is preferably greater than or equal to 5%, even 6% and / or less than or equal to 10%. It is included in practice between 5 and 8%.
  • the content of SrO is for its part preferably greater than or equal to 9%, even 10% and / or less than or equal to 17%. It is in practice between 12 and 16%
  • the sum of the contents of CaO, MgO, BaO and SrO is preferably greater than or equal to 23%, even 25%, and even 27% or 30%.
  • Zinc oxide is essential in the context of the compositions according to the invention because it makes it possible to increase the forming margin very considerably. Glasses devoid of zinc oxide also exhibit undesirable demixing, manifesting themselves in an opalescent appearance. It has also appeared that this oxide confers bacteriostatic properties, which is particularly advantageous in odontological applications.
  • the ZnO content is therefore preferably greater than or equal to 1%, even 2% and / or less than or equal to 6%. It is in practice between 2 and 5%.
  • the alkaline oxides (Li 2 O, Na 2 O, K 2 O) can be introduced into the compositions of the glass strands according to the invention to limit devitrification and reduce the viscosity of the glass.
  • the content of alkaline oxides must however remain less than or equal to 5% to avoid a penalizing decrease in the hydrolytic resistance of the glass and the forming margin.
  • the Na 2 O content is preferably greater than or equal to 1%. In practice, the Na 2 O + K 2 O + Li 2 O content is between 1.5 and 2%.
  • Titanium oxide (TiO 2 ) is an essential component of the composition according to the invention.
  • it makes it possible to improve the mechanical strength and the resistance to corrosion, in both acidic and basic environments.
  • the ultraviolet absorption due to the high titanium content can be unacceptable when the fibers are intended to reinforce polymers whose crosslinking is carried out by means of UV radiation.
  • titanium oxide tends to impart a yellow color to the fiber, which is a drawback for the dental applications that are the subject of the application.
  • the titanium oxide content of the glasses according to the invention is preferably less than 12%. It is in practice between 5 and 10%.
  • One or more other components may also be present, generally as impurities, in the chemical composition of the yarns according to the invention, the total content of these other components generally remaining less than or equal to 5%, preferably less than 3%. or 2%, the rate of each of these other components not generally exceeding 2% or 1%.
  • It may be in particular agents used to refine the glass (eliminate gaseous inclusions) such as sulfur, arsenic, halogens such as chlorine or cerium oxide, or compounds from the dissolution in glass small amounts of materials used as refractory in the glass melting furnace.
  • These different impurities do not modify the manner in which the glass threads described above solve the technical problem underlying the invention. It may also be compounds such as MnO, F, U 2 O, Fe 2 O 3 , B 2 O 3 , ZrO 2, the amount of which does not exceed 0.1% by weight of the composition.
  • the content of manganese oxide is preferably less than or equal to 1%, and preferably less than or equal to 0.3%, this oxide being capable of conferring on the glass a very intense violet coloring, the rate of MnO is preferably maintained at less than or equal to 0.1%, or even 0.05% and even 0.01%.
  • Fluorine may be added in small amounts to enhance the melting of the glass, or be present in the impurity state. For reasons related to the protection of the environment, the fluorine content is advantageously maintained below 1%, or even 0.5%, and especially less than 0.1%.
  • Iron oxide is an unavoidable impurity of the glasses according to the invention because of its presence in several raw materials, and its content is generally less than 0.5%. Since the staining effect generally attributed to titanium is in fact due to an electronic transfer between the Fe 2+ and Ti 4+ ions, the iron content in the glasses according to the invention is advantageously less than 0.3%. , especially at 0.2%, thanks to a judicious choice of raw materials.
  • Boric oxide or boric anhydride may be present in the composition according to the invention, generally at contents of less than or equal to 3%, preferably 1%.
  • the glass yarn according to the invention preferably does not contain B 2 O 3 .
  • the sum of the fluorine, boron oxide and lithium oxide (F + B 2 O 3 + Li 2 O) contents is less than or equal to 2% or even 1%.
  • the glass strands according to the invention are generally obtained from the glasses of composition previously described according to the following method: a multiplicity of molten glass threads, flowing from a multiplicity of orifices dispersed at the base of one or several dies are drawn in the form of one or more continuous filament webs and then gathered into one or more yarns collected on a moving support. It can be a support rotating when the son are collected in the form of windings or a support in translation when the son are cut by a member also serving to stretch or when the son are projected by an organ to stretch them to form a mat.
  • the yarns obtained, possibly after other processing operations, can thus be in various forms: continuous yarns, chopped or ground yarns, braids, ribbons, mats, nets, these yarns being composed of filaments of diameter that can go from about 5 to about 30 microns.
  • the molten glass feeding the dies is obtained from raw materials possibly pure (for example from the chemical industry) but most often natural, the latter sometimes including trace impurities, these raw materials being mixed in. appropriate proportions to obtain the desired composition, and then being melted.
  • the temperature of the molten glass (and therefore its viscosity) is set in the traditional way by the operator so as to allow the fibering of the glass, avoiding in particular the problems of devitrification and so as to obtain the best possible quality of the glass son.
  • the filaments are generally coated with a sizing composition which makes it possible to protect against abrasion and facilitate their subsequent association with materials to be reinforced.
  • the glass threads of the invention are intended to constitute reinforcing fibers of various prosthetic elements which are either made from rods consisting of glass fibers embedded in a resin matrix or made from fibers. of glass impregnated with a polymerizable matrix only at the time of the intervention by the practitioner.
  • the glass fiber content represents between 50 and 70% by volume, advantageously between 60 and 68% by volume of the prosthetic element.
  • prepreg polymerizable resin
  • Table 1 gathers examples according to the invention.
  • the composition of the glasses is expressed as a mass percentage of oxides, resulting from the analysis. It may also contain some impurities whose content is less than 0.1%.
  • the table has three basic properties: the temperature corresponding to a viscosity of 103 poise (102 Pa.s), denoted “T3", measured according to the ISO 7884-2 standard and expressed in degrees Celsius, close to the temperature of the glass in the die, - the forming margin or difference between the temperature "T3" and the liquidus temperature, denoted “delta T” and expressed in degrees Celsius, Table 1 Ex 1 2 3 4 5 SiO 2 54.5 48.7 53.0 50.8 53.8 BaO 6.5 6.0 6.0 7.0 6.0 SrO 13.0 14.0 13.0 13.0 12.0 ZnO 3.0 4.0 4.0 3.0 2.0 Al 2 O 3 3.7 3.7 3.7 3.7 CaO 5.4 5.4 5.4 6.0 6.0 MgO 5.4 6.7 5.4 6.0 7.0 TiO 2 7.0 9.7 8.0 9.0 8.0 Na 2 O 1.2 1.2 1.2 1.2 K 2 O 0.5 0.5 0.5 0.5 T3 (°
  • Radio-opacity has been assigned to the AR fiber. Radio-opacity reduced to 100% Ech 1 Ech 2 Ech 3 Ech 4 Average AR ring 100 100 100 100 100% bulrush 129 126 143 146 136% Ring II 132 134 146 149 140% Bangle III 139 131 152 156 145%

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Dental Preparations (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (12)

  1. Glasfaser, die zum Verstärken von Polymermaterialien geeignet ist und mehrere Filamente umfasst, deren chemische Zusammensetzung die folgenden Bestandteile in den nachstehend definierten, in Gewichtsprozent ausgedrückten Grenzen umfasst: SiO2 40 bis 60 Al2O3 0 bis 5 CaO 1 bis 15 MgO 1 bis 15 BaO 2 bis 15 SrO 12 bis 20 ZnO 0,5 bis 10 Na2O + K2O + Li2O 0 bis 5 TiO2 3 bis 20
  2. Glasfaser nach Anspruch 1, der Art, bei welcher der Gehalt an SiO2 zwischen 48 und 55% beträgt.
  3. Glasfaser nach Anspruch 1 oder 2, der Art, bei welcher der Gehalt an CaO zwischen 5 und 6% beträgt.
  4. Glasfaser nach einem der vorhergehenden Ansprüche, der Art, bei welcher der Gehalt an MgO zwischen 4 und 7% beträgt.
  5. Glasfaser nach einem der vorhergehenden Ansprüche, der Art, bei welcher der Gehalt an BaO zwischen 5 und 8% beträgt.
  6. Glasfaser nach einem der vorhergehenden Ansprüche, der Art, bei welcher der Gehalt an SrO zwischen 12 und 16% beträgt.
  7. Glasfaser nach einem der vorhergehenden Ansprüche, der Art, bei welcher die Summe des Gehalts an CaO, MgO, BaO und SrO größer oder gleich 23% ist.
  8. Glasfaser nach einem der vorhergehenden Ansprüche, der Art, bei welcher der Gehalt an ZnO zwischen 2 und 5 % beträgt.
  9. Glasfaser nach einem der vorhergehenden Ansprüche, der Art, bei welcher der Gehalt an TiO2 zwischen 5 und 10% beträgt.
  10. Prothetisches Dentalelement, das aus einem Verbundmaterial besteht, das die Glasfasern, die Gegenstand eines der Ansprüche 1 bis 9 sind, in ein Harz eingebettet, umfasst.
  11. Prothetisches Element nach Anspruch 10, dadurch gekennzeichnet, dass es sich um Dentalstifte, Interdentalstifte, Brückenverstärkungen oder Vorformen von CFAO handelt.
  12. Prothetisches Element nach Anspruch 10, dadurch gekennzeichnet, dass die Glasfasern volumenmäßig zwischen 50 und 70% des prothetischen Elements darstellen.
EP08829145A 2007-08-28 2008-08-28 Neue röntgendichte glasfasern und zahnprothesenelement mit diesen fasern Active EP2181074B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0757212A FR2920427B1 (fr) 2007-08-28 2007-08-28 Fils de verre aptes a renforcer des matieres organiques et/ou inorganiques
PCT/FR2008/051536 WO2009030859A2 (fr) 2007-08-28 2008-08-28 Nouvelles fibres de verre radio-opaques et element prothetique dentaire contenant lesdites fibres

Publications (2)

Publication Number Publication Date
EP2181074A2 EP2181074A2 (de) 2010-05-05
EP2181074B1 true EP2181074B1 (de) 2013-04-03

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EP08829145A Active EP2181074B1 (de) 2007-08-28 2008-08-28 Neue röntgendichte glasfasern und zahnprothesenelement mit diesen fasern

Country Status (4)

Country Link
US (1) US8298973B2 (de)
EP (1) EP2181074B1 (de)
FR (1) FR2920427B1 (de)
WO (1) WO2009030859A2 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8999871B2 (en) * 2011-05-25 2015-04-07 Nippon Electric Glass Co., Ltd. High refractive index glass

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2654612B1 (fr) 1989-11-20 1997-05-09 Marc Reynaud Tenon d'ancrage dentaire physiologique en materiau composite et son procede de fabrication.
CA2061502A1 (en) * 1991-02-19 1992-08-20 Kawamoto Toru Chemical resistant glass fiber composition
FR2727020B1 (fr) * 1994-11-21 1997-01-24 Marc Reynaud Element prothetique, et notamment tenon dentaire en materiau composite
EP0895774A3 (de) 1997-08-06 2002-01-30 JENERIC/PENTRON Incorporated Röntgenopake Dentalverbundwerkstoffe
US6686304B1 (en) * 1999-05-28 2004-02-03 Ppg Industries Ohio, Inc. Glass fiber composition
FR2796830B1 (fr) 1999-07-30 2001-12-28 Soc D Rech S Tech Dentaires Tenon dentaire transparent et radio-opaque
US7144633B2 (en) * 2002-07-29 2006-12-05 Evanite Fiber Corporation Glass compositions
JP2005170720A (ja) * 2003-12-10 2005-06-30 Asahi Glass Co Ltd 陰極線管パネルガラス

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Publication number Publication date
US8298973B2 (en) 2012-10-30
FR2920427B1 (fr) 2009-11-20
US20110045440A1 (en) 2011-02-24
WO2009030859A3 (fr) 2009-04-30
FR2920427A1 (fr) 2009-03-06
EP2181074A2 (de) 2010-05-05
WO2009030859A2 (fr) 2009-03-12

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